KR101784036B1 - Polysiloxane composition and pattern-forming method - Google Patents

Abstract

The present invention relates to a polysiloxane composition containing a nitrogen-containing compound having at least one group selected from the group consisting of [A] a polysiloxane, [B] a nitrogen-containing heterocyclic structure, and a polar group and an ester group. [C] It is preferable to further contain a compound which generates an acid by at least one of irradiation with ultraviolet rays and heating. The compound [B] is preferably a compound having a polar group and an ester group. The compound [B] preferably has at least one kind of group selected from the group consisting of a hydroxyl group and a carboxyl group as a polar group.

Description

POLYSILOXANE COMPOSITION AND PATTERN-FORMING METHOD [0002]

The present invention relates to polysiloxane compositions and methods of pattern formation. Specifically, the present invention relates to a polysiloxane composition suitable as a composition for forming a resist lower layer film, and a pattern forming method using the polysiloxane composition.

For pattern formation in the production of semiconductor devices and the like, a process of etching an organic or inorganic material located under the resist pattern using the resist pattern obtained by developing the resist film is often used. In such a process, there may arise a problem that the resist pattern is peeled off from the lower layer material or the lower layer material is dissolved by a developer developing the resist film. Further, since the etching rate of the resist pattern and the lower layer material is approximate, it is not possible to finely process the material of the lower layer, and a problem that the lower layer material is damaged when the resist pattern is removed by oxygen ashing may occur.

In order to solve the above problem, an inorganic resist undercoat film is provided between the resist film and the material of the lower layer, the lower resist film is etched using the resist pattern as a mask, and the lower layer material (See International Publication No. 2006/126406).

However, as the pattern becomes finer, the resist underlayer film has a higher performance, that is, the substrate reflectance is lower, the resist remnants in the removal of the resist film during development are smaller, resistance to alkaline developer and oxygen- Is required to be excellent. In order to further improve the pattern formed on the substrate to be processed, the resist pattern formed on the resist lower layer film is required to have excellent pattern collapse resistance and excellent pattern shape. However, the above-mentioned conventional techniques can not sufficiently satisfy this demand.

International Publication No. 2006/126406

The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a resist composition which has low substrate reflectance, fewer resist residues, excellent in pattern alkaline resistance and oxygen ashing resistance, A polysiloxane composition capable of forming a resist pattern, and a pattern forming method using the polysiloxane composition.

In order to solve the above problems,

[A] polysiloxane, and

(B) a compound having at least one group selected from the group consisting of a nitrogen-containing heterocyclic structure and a polar group and an ester group (hereinafter also referred to as "[B] compound"),

≪ / RTI >

The polysiloxane composition of the present invention makes it possible to form a resist pattern having excellent pattern collapse resistance and good pattern shape on the silicon-containing film formed of the polysiloxane composition by containing the [B] compound in addition to the [A] polysiloxane . The reason why the polysiloxane composition contains the [B] compound shows the above effect is not necessarily clear. For example, in post-exposure baking (PEB), diffusion of an acid in the resist film via the silicon- Since the compound [B] has at least one kind of group selected from the group consisting of a polar group and an ester group, sublimation thereof is suppressed during baking to form a silicon-containing film and remains in the silicon-containing film, It is possible to think about what can be exercised.

The polysiloxane composition

[C] A compound which generates an acid by at least one of irradiation with ultraviolet rays and heating (hereinafter also referred to as "[C] compound"))

Is further preferable.

According to the polysiloxane composition, by further containing the [C] compound, it is possible to obtain a resist pattern having excellent pattern decay resistance on the silicon-containing film to be formed, not only in the case of forming a resist pattern using an alkali development but also in an organic solvent development, It becomes possible to form a good resist pattern.

The [B] compound is preferably a compound having a polar group and an ester group. According to the polysiloxane composition, since the compound [B] has both a polar group and an ester group, its sublimation can be further suppressed at the time of baking the silicon-containing film, so that the above effect is more effectively exhibited.

The compound [B] is preferably a compound having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group as a polar group. According to the polysiloxane composition, since the [B] compound has the specific group, the sublimation can be further suppressed at the time of baking the silicon-containing film, so that the above effect is more effectively exhibited.

The compound [B] is preferably an ester group having a group represented by the following formula (i) and having a structure in which the group is bonded to a nitrogen atom.

(Wherein R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, provided that R ¹ and R ² are bonded to each other, Together with the carbon atoms to which they are bonded, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, and * denotes a bonding site with a nitrogen atom)

The compound having the above specific structure dissociates -CR ¹ R ² R ³ group by the action of an acid to generate a basic amino group. Therefore, by using such a compound as the [B] compound, the polysiloxane composition is excellent in storage stability even in a solution state.

The [B] compound is preferably a compound represented by the following formula (1).

(Wherein R ¹ , R ² and R ³ are the same as in the above formula (i), Z is an (n + 2) -valent group forming a heterocyclic structure together with the nitrogen atom, A is a single bond Or a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁴ is a hydroxyl group or a carboxyl group, n is an integer of 1 to 6, and when A and R ⁴ each are plural, a plurality of A and R ⁴ are each the same or different You can do it)

By having the specific structure of the [B] compound, the polysiloxane composition can form a resist pattern having excellent pattern collapse resistance and good pattern shape on the film. In addition, the polysiloxane composition is excellent in storage stability even in a solution state.

The polysiloxane [A] preferably contains a hydrolysis-condensation product of a compound represented by the following formula (S-1) (hereinafter also referred to as "compound (S1)").

(In the formula (S-1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, an alkenyl group or an aryl group, and a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, X is a halogen atom or OR ^A , R ^A is a monovalent organic group, a is an integer of 0 to 3, with the proviso that R ⁵ and X are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, A plurality of R < ⁵ > s and X's may be the same or different,

When the [A] polysiloxane is used as the hydrolysis condensate of the specific compound, the pattern collapse resistance and the pattern shape of the resist pattern formed on the silicon-containing film obtained from the polysiloxane composition are improved.

X in the above formula (S-1) is preferably OR ^A. By obtaining the polysiloxane [A] from the compound having the above specific structure, the hydrolysis and condensation reaction can be progressed appropriately. As a result, the resist pattern formed on the silicon-containing film obtained from the polysiloxane composition has a pattern- The fitness is further improved.

The content of the [B] compound to 100 parts by mass of the [A] polysiloxane is preferably 0.1 parts by mass or more and 30 parts by mass or less. By setting the content of the [B] compound to the above-specified range, the resist pattern formed on the silicon-containing film formed of the polysiloxane composition is further improved in pattern collapse resistance and pattern shape stability.

The content of the [C] compound relative to 100 parts by mass of the [A] polysiloxane is preferably 0.1 part by mass or more and 30 parts by mass or less. By setting the content of the [C] compound to the above-specified range, the resist pattern formed on the silicon-containing film formed of the polysiloxane composition in pattern formation by the organic solvent development is further improved in pattern collapse resistance and pattern shape well .

The polysiloxane composition preferably also contains water. Since the polysiloxane composition further contains water, the storage stability is further improved because the [A] polysiloxane is hydrated.

Since the polysiloxane composition has the above-described characteristics, it can be suitably used for forming a resist underlayer film.

The pattern forming method of the present invention comprises

(1) a step of applying the polysiloxane composition onto a substrate to form a silicon-containing film, (2) a step of applying a resist composition on the silicon-containing film to form a resist film, (3) (4) a step of developing the exposed resist film to form a resist pattern, and (5) a step of forming a resist pattern by using the resist pattern as a mask to expose the silicon- Step of sequentially etching the substrate by dry etching

Respectively.

According to the above pattern forming method, by using the polysiloxane composition, a resist pattern having excellent pattern collapse resistance and good pattern shape can be formed, and as a result, a desired pattern can be faithfully transferred to the processed substrate with good reproducibility .

In the above pattern forming method, it is preferable that the polysiloxane composition further contains a compound which generates an acid by at least one of [C] irradiation with ultraviolet rays and heating.

In the above-mentioned pattern formation method, even when the polysiloxane composition further contains the [C] compound, even when the resist pattern is formed by organic solvent development, a resist pattern having excellent pattern collapse resistance and good pattern shape can be formed , And as a result, a desired pattern can be faithfully transferred to the processed substrate with good reproducibility.

As described above, according to the polysiloxane composition and the pattern forming method of the present invention, it is possible to provide a polysiloxane composition which is low in substrate reflectance, low in resist residues, excellent in pattern alkali resistance and oxygen ashing resistance, A good resist pattern can be formed. As a result, the desired pattern can be faithfully transferred to the processed substrate with good reproducibility.

≪ Polysiloxane composition >

The polysiloxane composition contains [A] polysiloxane and [B] compound. The polysiloxane composition may contain, as a suitable component, [C] compound, [D] solvent and [E] water. In addition, the polysiloxane composition may contain other optional components as long as the effect of the present invention is not impaired. Hereinafter, each component will be described.

<[A] Polysiloxane>

[A] Polysiloxane is a polymer or oligomer having siloxane bonds. The polysiloxane [A] is not particularly limited as long as it has the above structure, and examples thereof include hydrolysis condensates of hydrolyzable silane compounds. Examples of the hydrolyzable silane compound include the above compound (S1) and the following compound (S2). These hydrolyzable silane compounds may be used alone or in combination of two or more.

The compound (S1) is a compound represented by the above formula (S-1).

In the above formula (S-1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, an alkenyl group or an aryl group. Some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, a cyano group, an aryl group which may be substituted or an alkoxy group having an oxetane ring. X is a halogen atom or OR ^A ; R ^A is a monovalent organic group. a is an integer of 0 to 3; Provided that when R ⁵ and X are each plural, plural R ⁵ and X may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁵ include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group and n-pentyl group; And branched alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl and isoamyl groups.

Examples of the alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom represented by R ⁵ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoroethyl group, a perfluoroethyl group, a purple A perfluorobutyl group, a perfluoropentyl group, and the like.

Examples of the alkyl group substituted with a cyano group represented by R ⁵ include a cyanoethyl group and a cyanopropyl group.

Examples of the alkyl group substituted with an optionally substituted aryl group represented by R ⁵ include a benzyl group, a phenethyl group, a phenylpropyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a phenoxybenzyl group, A dimethylaminobenzyl group, and an acetylaminobenzyl group.

Examples of the alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having an oxetane ring represented by R ⁵ include a 3-alkyl-substituted 3-oxetanylalkoxyalkyl group, a 2-alkyl-substituted 3-oxetanylalkoxyalkyl group , 3-oxetanylalkoxyalkyl group and the like.

Examples of the alkenyl group represented by R ⁵ include vinyl, allyl, methallyl, butenyl, pentenyl, and hexenyl. Of these, groups represented by the following formula (a) are preferable.

In the above formula (a), m is an integer of 0 to 4. * Represents a bonding site to a silicon atom.

The above-mentioned m is preferably 0 or 1, more preferably 0.

Examples of the aryl group represented by R ⁵ include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Among them, a phenyl group and a methylphenyl group are preferable.

Among these, preferable as R ⁵ is an unsubstituted alkyl group, an alkyl group substituted with an alkoxy group having an oxetane ring, or an aryl group, and an alkyl group having 1 to 3 carbon atoms, a 3-alkyl substituted 3-oxetanylalkoxyalkyl group, a substituted or unsubstituted More preferably a methyl group, a 3-ethyl-3-oxetanylmethoxypropyl group, a phenyl group, or a methylphenyl group.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

A monovalent organic group represented by R ^A of the OR ^A indicated by the X is, for example, an alkyl group, and the like can be mentioned an aryl group, an alkylcarbonyl group.

Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-butyl group.

Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkylcarbonyl group include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group.

Roneun the X, among these, from the viewpoint that goes to the hydrolysis and condensation reactions suitable rate of the compound (S1), ^A is OR, and more preferably the alkoxy group is more preferred, and a methoxy group, an ethoxy group.

The above-mentioned "a" is preferably an integer of 0 to 2, preferably 1 or 2, and more preferably 1.

Examples of the compound (S1) include a case where a is 0, such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- , Tetra-sec-butoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, tetrachlorosilane and the like.

Examples of the compound (S1) include a case where a is 1, and examples thereof include phenyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane , 4-methoxyphenyltrimethoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3- 3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxyphenyltrimethoxysilane, 2-hydroxyphenyl tri 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylaminophenyltrimethoxysilane, 2,4,6-trimethylphenyltrimethoxysilane, 4-methylbenzyl 4-hydroxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-aminobenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, Containing silane such as 4-dimethylaminobenzyltrimethoxysilane and 4-acetylaminobenzyltrimethoxysilane;

Methyltriethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri- methyltris (methylethylketoxime) silane, methyltris (dimethylsiloxane) silane, methyltriethoxysilane, methyltrialkoxysilane, methyltriisopropoxysilane, methyltris Silane, methyltris (methoxyethoxy) silane, methyltris (trimethylsiloxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri- Butoxysilane, ethyltri-sec-butoxysilane, ethyltri-t-butoxysilane, ethyltriphenoxysilane, ethyldichlorosilane, ethyltriacetoxysilane, ethyltrichlorosilane , Ethyltris (trimethylsiloxy) silane, n-propyltrimethoxysilane, n-propyltriethoxysilane Propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-i-propoxysilane, n-propyltriethoxysilane, n-propyltrichlorosilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltriethoxysilane, i-propyltri-i-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i- propyltriethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane, n-butyl Butyl tri-sec-butoxysilane, n-butyl tri-t-butoxysilane, n-butyltriphenoxysilane, n-butyl trichlorosilane, Methoxysilane, 2-methylpropyltriethoxysilane, 2-methylpropyl Methylpropyltri-sec-butoxysilane, 2-methylpropyltri-i-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2- methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltri- methylpropyltri-sec-butoxysilane, 1-methylpropyltri-t-butoxysilane, 1-methylpropyltriphenoxy Silane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-i-propoxysilane, t-butyltri-n-butoxysilane silane-containing silanes such as t-butyltris-sec-butoxysilane, t-butyltri-t-butoxysilane, t-butyltriphenoxysilane, t-butyltrichlorosilane and t-butyldichlorosilane;

Vinyltriethoxy silane, vinyl tri-n-butoxy silane, vinyl tri-sec-butoxy silane, vinyl tri-n-propoxy silane, t-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri- Silane-containing silanes such as silane, allyltri-sec-butoxysilane, allyltri-t-butoxysilane and allyltriphenoxysilane;

Ethyl-3-oxetanylmethoxypropyltriethoxysilane, 3-ethyl-3-oxetanylmethoxypropyltrimethoxysilane, 3-methyl-3-oxetanylmethoxypropyltrimethoxysilane, 3- Methyl-3-oxetanylethoxypropyltrimethoxysilane, 3-ethyl-3-oxetanylmethoxyethyltriethoxysilane, and the like.

Examples of the compound (S1) include a case where a is 2, such as diphenyldimethoxysilane, di (4-methylphenyl) dimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldichlorosilane, di 4-methylphenyl) dichlorosilane, dimethyldichlorosilane, and diethyldichlorosilane.

Examples of the compound (S1) include a case where a is 3, such as triphenylmethoxysilane, tri (4-methylphenyl) methoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triphenylchlorosilane, tri 4-methylphenyl) chlorosilane, trimethylchlorosilane, triethylchlorosilane, and the like.

Of these, from the viewpoints of reactivity and ease of handling of materials, there are phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane methyltrimethoxysilane Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- Butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-sec-butoxysilane, ethyl tri-n-propoxy silane, ethyl tri- Propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i-propoxysilane, n-propyltri-n-butoxysilane, n- vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane are preferable, and a phenoxy silane Trimethoxysilane, 4-methylphenyl trimethoxysilane, methyltrimethoxysilane, 3-ethyl-3-oxetanyl -dihydroxy-20 is more preferred for the silane propyltriethoxysilane.

Among these, tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint that the polysiloxane composition can form a silicon-containing film excellent in dry etching resistance.

The compound (S2) is a compound represented by the following formula (S-2).

In the above formula (S-2), R ⁶ and R ¹² are each independently a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or an alkylcarbonyloxy group. R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently a monovalent organic group or a halogen atom. R ⁹ is an arylene group, a methylene group or an alkylene group having 2 to 10 carbon atoms. and b is an integer of 0 to 3. When R ⁹ is plural, a plurality of R ⁹ may be the same or different. p is an integer of 1 to 20;

Examples of the halogen atom represented by R &lt; ⁶ &gt; and R &lt; ¹² &gt; include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkoxy group represented by R ⁶ and R ¹² include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a n-butoxy group, N-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n- -Decyloxy group, and the like.

Examples of the aryloxy group represented by R ⁶ and R ¹² include a phenoxy group, a 4-methylphenoxy group, and a naphthyloxy group.

Examples of the alkylcarbonyloxy group represented by R ⁶ and R ¹² include a methylcarbonyloxy group, an ethylcarbonyloxy group, and a propylcarbonyloxy group.

As R ⁶ and R ¹² , an alkoxy group is preferable, a methoxy group and an ethoxy group are more preferable, and an ethoxy group is more preferable.

Examples of the monovalent organic group represented by R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ include an alkyl group, an alkoxy group, an aryl group, an alkenyl group, and a group having a cyclic ether structure. Some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl and t-butyl. Examples of the fluorine atom-substituted alkyl group include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoroethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a hexafluoro-i-propyl group And the like.

Examples of the alkoxy group include groups similar to the examples of the alkoxy group represented by R ⁶ and R ¹² .

The aryl group includes, for example, phenyl, naphthyl, methylphenyl, benzyl, phenethyl, ethylphenyl, chlorophenyl, bromophenyl and fluorophenyl.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, a 3-butenyl group, a 3-pentenyl group and a 3-hexenyl group.

Examples of the group having a cyclic ether structure include groups having an oxiranyl group such as an oxiranyl group, a glycidyl group, a glycidyloxy group, and a glycidyloxypropyl group; A group having an oxetanyl group such as an oxetanyl group, an oxetanylmethyl group, an oxetanylmethoxy group and a 3-ethyl-3-oxetanylmethoxypropyl group; A group having a tetrahydrofuranyl group such as a tetrahydrofuranyloxy group or a tetrahydrofuranylmethoxy group; And groups having a tetrahydropyranyl group such as a tetrahydropyranyloxy group and a tetrahydropyranylmethoxy group.

Among these, R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkoxy group, more preferably a methoxy group or an ethoxy group, and particularly preferably an ethoxy group.

Examples of the arylene group represented by R ⁹ include a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a chlorophenylene group, a bromophenylene group, and a fluorophenylene group. Of these, a phenylene group is more preferable.

Examples of the alkylene group having 2 to 10 carbon atoms represented by R ⁹ include an ethylene group, a propylene group and a butylene group.

As R ^9, an arylene group is preferable, and a phenylene group is more preferable.

The b is preferably 1 or 2, more preferably 1.

The p value is preferably 1 to 15, more preferably 1 to 10.

As the compound (S2), for example, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1 , 2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy- -Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1 , 2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy- - phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2 , 2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy- Diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1 , 1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyldisilane;

1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy- 1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyl di Silane, 1,1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2- Triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2 -Tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2 -Dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2 , 2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 2-diphenoxy-1,1,2,2-tetraphenyldisilane;

Bis (tri-n-propoxysilyl) methane, bis (trimethoxysilyl) methane, bis (tri-n-propoxysilyl) Bis (tri-sec-butoxysilyl) methane, bis (tri-t-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) Bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) Ethane, 1,2-bis (tri- sec-butoxysilyl) ethane, 1,2-bis (tri-t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) ) Methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) (Di-i-propoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane , 1- (di-t-butoxymethylsilyl) -1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) Propanedimethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-i-propoxy) (Di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di- Butoxymethylsilyl) -2- (tri-sec-butoxysilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (tri-t-butoxysilyl) ethane;

Bis (di-n-propoxymethylsilyl) methane, bis (di-i-propoxymethylsilyl) methane, bis (di- (Di-sec-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2- Bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2- ), Methane, bis (dimethylethoxysilyl) methane, bis (dimethyl-n-propoxysilyl) methane, bis (dimethyl- Dimethyl-sec-butoxysilyl) methane, bis (dimethyl-t-butoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, (Dimethyl-n-propoxysilyl) ethane, 1,2-bis (dimethyl-n-propoxysilyl) ethane, 1,2- Silane) ethane, 1,2-bis (dimethyl-sec-butoxysilyl) ethane, 1,2-bis (dimethyl-t-butoxysilyl) ethane;

1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) 1- (trimethylsilyl) methane, 1- (di-n-butoxymethylsilyl) -1- 1- (trimethylsilyl) methane, 1- (di-t-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (Trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di- 2- (trimethylsilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2 (trimethylsilyl) - (trimethylsilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (trimethylsilyl) ethane;

Bis (triethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t-butoxysilyl) benzene, (Tri-n-propoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3- (Tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxy) (Tri-sec-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, Benzene, 1,4-bis (tri-t-butoxysilyl) benzene;

And polycarbosilanes such as polydimethoxymethylcarbosilane, polydiethoxymethylcarbosilane, and the like.

Among these, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2- Dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, Tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2- Bis (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (Methoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, Ethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane Bis (dimethylethoxysilyl) methane, bis (dimethylethoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2- 1- (trimethylsilyl) methane, 1- (trimethylsilyl) methane, 1- (trimethylsilyl) Bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) Benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, polydimethoxymethylcarbosilane, (Trimethoxysilyl) benzene and 1,4-bis (triethoxysilyl) benzene are more preferable, and 1,4-bis (triethoxysilyl) benzene Is more preferable.

The polysiloxane [A] preferably contains the hydrolysis-condensation product of the compound (S1) from the viewpoint of further improving the pattern collapse resistance and pattern shape of the resist pattern formed on the silicon-containing film, 0, and a hydrolysis-condensation product of the compound (S1) in which a is an integer of 1 to 3, are more preferable.

The content of [A] polysiloxane is usually 70 mass% or more, preferably 80 mass% or more, and more preferably 90 mass% or more, relative to the total solid content in the polysiloxane composition.

The [A] polysiloxane may be contained alone or in combination of two or more.

<Synthesis method of [A] polysiloxane>

[A] The polysiloxane can be synthesized, for example, by hydrolysis and condensation of a hydrolyzable silane compound such as the compound (S1), the compound (S2) and the like by a known method.

The weight average molecular weight (Mw) of the polysiloxane [A] in terms of polystyrene by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 2,000 to 100,000, more preferably 2,000 to 50,000, still more preferably 2,000 to 30,000 , And particularly preferably from 2,000 to 10,000.

The Mw of the polysiloxane [A] in the present specification is a value measured by GPC under the following conditions.

GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (made by Tosoh)

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Column temperature: 40 DEG C

Standard material: monodisperse polystyrene

&Lt; [B] Compound >

The [B] compound is a nitrogen-containing compound having at least one group selected from the group consisting of a nitrogen-containing heterocyclic structure and a polar group and an ester group. By containing the [B] compound, the polysiloxane composition improves the pattern collapse resistance of the resist pattern formed on the silicon-containing film, and the pattern shape becomes better. Although the reason why the polysiloxane composition contains the [B] compound is not necessarily clear, for example, the [B] compound is present in the silicon-containing film under the resist film so that the silicon- Diffusion of an acid in the resist film through the resist film can be suppressed. This effect is significant compared to amine compounds that do not have both polar and ester groups. The reason for this is considered to be that the above effect is sufficiently exhibited because the [B] compound having a polar group and / or an ester group is suppressed from sublimation during baking at the time of forming a silicon containing film and remains in the silicon containing film. Further, it is considered that the polysiloxane composition has a nitrogen-containing heterocyclic structure as the [B] compound, thereby improving storage stability.

Examples of the nitrogen-containing heterocyclic structure include pyrrolidine structure, piperidine structure, morpholine structure, piperazine structure, homopiperazine structure, 1,4,7-triazacyclononane structure, 1,4 , 7,10-tetraazacyclododecane structure, and other aliphatic heterocyclic structures;

A pyrazole structure, a pyridine structure, a pyridine structure, a pyrimidine structure, a pyridazine structure, an indolizine structure, a quinoline structure, an imidazole structure, an imidazole structure, A nitrogen-containing heterocyclic structure such as an acyclic structure, a quinoline structure, an isoquinoline structure, a carbazole structure, an acridine structure, a phenazine structure, a phenoxazine structure, and an aromatic heterocyclic structure such as a triazine structure.

Among them, a piperidine structure, a pyrrolidine structure, an imidazole structure, a benzimidazole structure and a triazine structure are preferable, and a piperidine structure and a pyrrolidine structure are more preferable.

Examples of the polar group include a hydroxyl group, a carboxyl group, a cyano group, and an oxetanyl group. Of these, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is more preferable.

Examples of the ester group include an alkyl ester group, a cycloalkyl ester group, and an aryl ester group. Among them, an alkyl ester group and a cycloalkyl ester group are preferable, and it is more preferable that the group represented by the formula (i) is bonded to a nitrogen atom. The [B] compound having a structure in which the group represented by the above formula (i) is bonded to a nitrogen atom is a compound that dissociates -CR ¹ R ² R ³ groups by the action of an acid to generate a basic amino group, The composition has an effect that storage stability is excellent even in the form of a solution.

In the above formula (i), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. Provided that R ¹ and R ² may combine with each other to form a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms together with the carbon atoms to which they are bonded. * Represents a bonding site with a nitrogen atom.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² and R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i- have.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ¹ , R ² and R ³ include monocyclic cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cyclooctane and cyclodecane; And a bridged cycloalkane such as norbornane, tricyclodecane, tetracyclododecane, and adamantane, and the like, and the like. Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms which R ¹ and R ² bond together to form together with the carbon atom to which they are bonded include, for example, the groups represented by R ¹ , R ² and R ³ And groups in which one hydrogen atom bonded to the carbon atom of the bonding site of the monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms is excluded.

Examples of the monovalent group represented by -CR ¹ R ² R ³ in the above formula (i) include a t-butyl group, a t-amyl group, a 1-ethyl-1-methylpropyl group, Propyl group and the like, and groups represented by the following formulas (p-1) to (p-15). Among them, t-butyl group and t-amyl group are preferable from the viewpoint of ease of synthesis of [B] compound.

When the [B] compound is a compound having a nitrogen-containing heterocyclic structure, the polar group and the ester group may be bonded directly to the nitrogen-containing heterocycle or may be bonded to the nitrogen-containing heterocyclic ring via a linking group. Examples of the linking group include a divalent hydrocarbon group of 1 to 20 carbon atoms which may contain -O-, -CO-, -NH-, -SO ₂ - or the like between carbon-carbon bonds or carbon-hydrogen bonds.

The compound [B] includes, for example, a compound represented by the above formula (1) (hereinafter also referred to as "compound (1)"), a compound having a polar group and no ester group ), A nitrogen-containing compound having an ester group bonded to a nitrogen atom and having no polar group (hereinafter also referred to as "compound (3)") and the like.

In the above formula (1), R ¹ , R ² and R ³ are as defined in the above formula (i). Z is an (n + 2) -valent group which forms a heterocyclic structure together with a nitrogen atom. A is a single bond or a divalent hydrocarbon group having 1 to 8 carbon atoms. R ⁴ is a hydroxyl group or a carboxyl group. n is an integer of 1 to 6; When A and R &lt; ⁴ &gt; are plural each, plural A and R &lt; ⁴ &gt; may be the same or different.

Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms represented by A include divalent chain hydrocarbon groups such as methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-octylene group; And a bivalent alicyclic hydrocarbon group in which one hydrogen atom is removed from carbon atoms other than the carbon atom of the bonding site of the monovalent alicyclic hydrocarbon group represented by R ¹ , R ² and R ³ described above.

As n, 1 or 2 is preferable, and 1 is more preferable.

Examples of the compound (1) include compounds represented by the following formulas (1-1) to (1-5).

Among them, the above-mentioned formulas (1-1), (1-2), (1-4) and (1-5) are preferable.

Examples of the compound (2) include compounds represented by the following formulas (2-1) to (2-4).

In the formulas (2-2) and (2-3), each R is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Provided that at least one of the plurality of R in each formula is a hydrogen atom.

Of these, compounds represented by the above formula (2-1) are preferable.

Examples of the compound (3) include compounds represented by the following formulas (3-1) to (3-3).

Of these, compounds represented by the above formula (3-1) are preferable.

As the [B] compound, the compound (1) and the compound (2) are preferable, and the compound (1) is more preferable.

The content of the [B] compound in the polysiloxane composition is usually 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the [A] polysiloxane, and 1 part by mass Or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less. The [B] compounds may be used singly or in combination of two or more.

&Lt; Compound [C] >

The [C] compound is a compound which generates an acid by at least one of irradiation with ultraviolet rays and heating. The polysiloxane composition contains a [C] compound in addition to the above-mentioned [B] compound to form a pattern on a silicon-containing film to be formed, not only in the case of forming a resist pattern using an alkali development, It becomes possible to form a resist pattern having excellent decay resistance and good pattern shape. The reason why the polysiloxane composition further contains the [C] compound is not necessarily clear, but the resist pattern formed by, for example, organic solvent development may be a polymer having a polar group such as a carboxyl group And that an interaction occurs between the [C] compound and the acid present in the silicon-containing film, which is generated in exposure light during the formation of a resist pattern or in baking at the time of formation of a silicon-containing film .

Examples of the [C] compound include an onium salt compound such as a sulfonium salt, a tetrahydrothiophenium salt and an oiodonium salt, an N-sulfonyloxyimide compound, an organic halogen compound, a disulfone, a diazomethane sulfone Sulfone compounds and the like.

Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, sulfonium 2-bicyclo [2.2.1] hept-2-yl ethanesulfonate as -1,1,2,2- tetrafluoroborate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 ^{2,5 -7,10} ] dodecanyl) -1,1-difluoroethanesulfonate, triphenylsulfonium N, N'-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium salicylate Triphenylsulfonium salts such as ^silylate , triphenylsulfonium camphorsulfonate, and triphenylsulfonium tricyclo [3.3.1.1 ^3,7 ] decanyldifluoromethane sulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n- Octylsulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenyl 4-cyclohexylphenyldiphenylsulfonium N, N ', N'-tetramethyldicyclohexylphenylsulfonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) 4-cyclohexylphenyldiphenylsulfonium salts such as bis (nonafluoro-n-butanesulfonyl) imidate and 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro 4-t-butylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t- -Butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyldiphenyl 4-t-butylphenyldiphenylsulfonium salts such as sulfonium N, N'-bis (nonafluoro-n-butane sulfonyl) imidate and 4-t-butylphenyldiphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n- (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, perfluoro- , Tri (4-t-butylphenyl) sulfonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium N, N'-bis (nonafluoro-n-butane sulfonyl) imide and tri (4-t-butylphenyl) sulfonium camphorsulfonate. Butylphenyl) sulfonium salts, and the like.

Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- 1-yl) tetrahydrothiophenium perfluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro- - (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1 - (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N'-bis (nonafluoro-n-butane sulfonyl) imidate, 1- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt such as naphthalen-1-yl) -tetrahydrothiophenium camphorsulfonate;

(3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- Phenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5- Phenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (3,5-dimethyl (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N'-bis (nonafluoro-n-butane sulfonyl) imidate, 1- 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salts such as openium camphorsulfonate and the like.

Examples of the oiodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfo Diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (3-tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis (nonafluoro-n-butanesulfonyl) Dodecyliodonium salts such as dodecyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoro (4-t-butylphenyl) iodonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfone (4-t-butylphenyl) iodonium N, N'-bis (nonafluoro-n-butanesulfonyl) imidate, bis (4-t-butylphenyl) oiodonium camphorsulfonate, etc. (4-t-butylphenyl) iodonium salt of bis (4-t-butylphenyl).

Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, Imide, N- (2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonyloxy) succinimide, N- N-sulfonyloxy succinimides such as sulfonyloxy) succinimide;

(Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2 (Perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-en-2 , 3-dicarboxyimide, N- (2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonyloxy) bicyclo [2.2 -1,2] hept-5-ene-2,3-dicarboxyimide, and N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 2.2.1] hept-5-ene-2,3-dicarboxyimide and the like.

Among them, onium salt compounds are preferable, and sulfonium salts and oiodonium salts are more preferable, and triphenylsulfonium salts and bis (4-t-butylphenyl) oiodonium salts are more preferable as the [C] Phenylsulfonium trifluoromethanesulfonate, triphenylsulfonium tricyclo [3.3.1.1 ^3,7 ] decanyldifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate Is particularly preferable.

The [C] compounds may be used singly or in combination of two or more.

The content of the [C] compound in the polysiloxane composition is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 0.1 part by mass to 100 parts by mass, relative to 100 parts by mass of the polysiloxane [A] from the viewpoint that the pattern shape of the resist pattern to be formed becomes better. More preferably not less than 20 parts by mass, and most preferably not less than 0.1 parts by mass and not more than 10 parts by mass.

<[D] Solvent>

As the [D] solvent, any solvent can be used as long as it can dissolve and disperse the above-mentioned [A] polysiloxane, [B] compound and optional components to be contained as required.

Examples of the [D] solvent include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent, an amide-based solvent and a hydrocarbon-based solvent.

Examples of the alcohol solvent include alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, Butanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec- octanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, Monoalcohol solvents such as decyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol solvents such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; and the like.

Examples of the ether solvents include aliphatic ether solvents such as diethyl ether, dipropyl ether and dibutyl ether;

Aromatic ether solvents such as diphenyl ether and anisole;

And cyclic ether solvents such as tetrahydrofuran and dioxane.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, Aliphatic ketone solvents such as butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, 2,4-pentanedione and acetonyl acetone;

Aromatic ketone solvents such as acetophenone and ethyl phenyl ketone;

And cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone.

Examples of the amide solvent include N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, - methyl propionamide; and the like;

And cyclic amide solvents such as N-methylpyrrolidone and N, N'-dimethylimidazolidinone.

Examples of the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl propyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec- Acetic acid ethyl acetate, methyl propionate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, , N-butyl propionate, iso-amyl propionate, methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate;

Dicarboxylic acid diester solvents such as diethyl oxalate, di-n-butyl oxalate, diethyl malonate, dimethyl phthalate and diethyl phthalate;

Polyhydric alcohol diester solvents such as diacetic acid ethylene glycol and diacetic acid propylene glycol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Polyhydric alcohol partial ether acetate type solvents such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and methoxytriglycol acetate;

lactone solvents such as? -butyrolactone and? -valerolactone;

And carbonate-based solvents such as diethyl carbonate, propylene carbonate and the like.

Examples of the hydrocarbon solvent include n-pentane, iso-pentane, n-hexane, isohexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane;

Benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di- And aromatic hydrocarbon solvents such as amylnaphthalene.

Among these, alcohol solvents and ester solvents are preferable, and polyhydric alcohol partial ether solvents and polyhydric alcohol partial ether acetate solvents are more preferable, and propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate Is more preferable. [D] One or more solvents may be used as the solvent.

The content of alcohol having a boiling point of 100 占 폚 or less is preferably 20% by mass or less, more preferably 5% by mass or less, in the [D] solvent. Alcohols having a boiling point of 100 占 폚 or lower are sometimes generated during the hydrolysis and condensation of silane compounds such as the above-mentioned compounds (S1) and (S2), and it is preferable to remove them by distillation or the like in such a range.

<[E] water>

Since the polysiloxane composition contains water, the storage stability is improved because the [A] polysiloxane is hydrated. Further, when the polysiloxane composition contains water, the curing at the time of film formation from the polysiloxane composition is promoted, and a dense film can be obtained. The content of water in the polysiloxane composition is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, further preferably 0.2 to 10 parts by mass, per 100 parts by mass of the [D] solvent. The water content in the polysiloxane composition is preferably 0 to 30 mass%, more preferably 0.1 to 20 mass%, and still more preferably 0.2 to 10 mass%. If the content of water is excessively high, the storage stability of the polysiloxane composition and the uniformity of the formed silicon-containing film may be lowered.

<Other optional components>

The polysiloxane composition may contain, as other optional components, in addition to the above components [A] to [E], for example, [beta] -diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, can do. The polysiloxane composition may contain one or more other optional components.

The polysiloxane composition contains? -Diketone, whereby the coatability and storage stability are improved. Examples of? -diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5- 4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5 , 5-hexafluoro-2,4-heptanedione, and the like. The content of? -Diketone in the polysiloxane composition is preferably 66 parts by mass or less, more preferably 42% by mass or less based on 100 parts by mass of the [D] solvent. By setting the content of the? -Diketone in the above-mentioned range, the polysiloxane composition can attain a certain storage stability and reduce the likelihood that properties such as film uniformity will deteriorate. The? -diketone may be used singly or in combination of two or more species.

The colloidal silica is a dispersion in which a high-purity silicic anhydride is dispersed in a hydrophilic organic solvent. The average particle diameter is usually 5 to 30 nm, preferably 10 to 20 nm, and the solid content concentration is about 10 to 40 mass%. Examples of the colloidal silica include methanol silica sol, isopropanol silica sol (manufactured by Nissan Chemical Industries, Ltd.); Oscar (manufactured by Shokubai Chemical Industry Co., Ltd.) and the like.

Examples of the colloidal alumina include alumina sol 520, copper 100 and copper 200 (manufactured by Nissan Chemical Industries, Ltd.); Alumina clear sol, alumina sol 10, and alumina 132 (manufactured by Kawaken Fine Chemical Co., Ltd.).

Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, an acrylate compound, a methacrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, Arylene, polyamide, polyquinoxaline, polyoxadiazole, and fluorine-based polymers.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants .

The base generator is a compound which generates a base by performing a heat treatment or an exposure treatment. As the base generator, for example, a triphenylsulfonium compound; Triphenylmethanol; Photoactive carbamates such as benzyl carbamate and benzoin carbamate; amides such as o-carbamoyl hydroxyl amide, o-carbamoyl oxime, aromatic sulfonamide, alpha-lactam, and N- (2-allylethynyl) amide; Oxime ester,? -Amino acetophenone, and cobalt complexes.

&Lt; Process for producing polysiloxane composition >

The polysiloxane composition can be prepared by, for example, mixing [A] a polysiloxane, a [B] compound, and optional components as required, and dissolving or dispersing in an organic solvent [D]. The solid concentration of the polysiloxane composition is usually 0.5% by mass to 20% by mass, and preferably 1% by mass to 15% by mass.

The use of the polysiloxane composition is not particularly limited, and the polysiloxane composition can be used as a film forming material such as an interlayer insulating film, a protective film, and an antireflection film. Particularly, the silicon-containing film obtained from the polysiloxane composition has high adhesion to a resist film or another underlayer film (antireflection film), and by using the silicon-containing film, a resist pattern having an excellent bottom shape with reduced slackness or the like on the film can be obtained Therefore, the polysiloxane composition can be suitably used as a composition for forming a resist lower layer film, for example, in a pattern forming method using a multilayer resist process such as the pattern formation method described later, and can be used in a region finer than 90 nm (ArF, in particular it can be suitably used in the ArF, F _2, EUV, a pattern forming method using the multi-layer resist process in the nano-imprint).

The silicon-containing film as the resist undercoat film can be formed by applying the polysiloxane composition to the surface of another lower layer film (antireflection film) or the like to form a coating film, and heating and curing the coating film.

Examples of the method of applying the polysiloxane composition include a spin coating method, a roll coating method, a dipping method, and the like. The temperature for heating the formed coating film is usually 50 to 450 ° C. The film thickness of the silicon-containing film obtained after the heat treatment is usually 10 to 200 nm.

&Lt; Pattern formation method >

The pattern forming method of the present invention comprises

(1) a step of applying the above polysiloxane composition onto a substrate to be processed to form a silicon-containing film (hereinafter also referred to as "step (1)"),

(2) a step of applying a resist composition on the silicon-containing film to form a resist film (hereinafter also referred to as "step (2)"),

(3) a step of selectively irradiating the photomask with light to expose the resist film (hereinafter also referred to as "step (3)"),

(4) a step of developing the exposed resist film to form a resist pattern (hereinafter also referred to as "step (4)") and

(5) a step of sequentially dry-etching the silicon-containing film and the substrate to be processed (hereinafter also referred to as "step (5)") using the resist pattern as a mask,

Respectively.

According to the above pattern forming method, by using the polysiloxane composition, a resist pattern having excellent pattern collapse resistance and a good pattern shape can be formed, and as a result, a desired pattern can be faithfully transferred to the processed substrate with good reproducibility. Hereinafter, each step will be described.

[(1) Process]

In the step (1), the polysiloxane composition is applied onto a substrate to form a silicon-containing film.

Examples of commercially available products include black diamond (AMAT), silk (Dow Chemical), LKD5109 (JSR), and the like. Examples of the substrate to be processed include silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, And a wafer coated with a low dielectric insulating film such as a silicon wafer or the like. As the substrate to be processed, a patterned substrate such as a wiring groove (trench) or a plug groove (via) may be used.

Further, another resist lower layer film (a resist lower layer film different from the silicon-containing film obtained from the polysiloxane composition) may be formed in advance on the substrate to be processed. As other resist underlayer films, for example, in order to further complement the functions of the silicon-containing film and / or the resist film in the resist pattern formation or to obtain functions not possessed by them, Film resistance, high etching resistance against fluorine gas such as CF ₄ ), and the like can be given. Commercially available products of the antireflection film as another resist underlayer film include, for example, NFC HM8006 (made by JSR).

As a method of applying the polysiloxane composition, for example, a spin coating method and the like can be given.

Examples of the method for forming the silicon-containing film include a method of curing the coating film of the polysiloxane composition by exposure and / or heating.

Examples of the radiation used for the exposure include electromagnetic waves such as visible light, ultraviolet light, deep ultraviolet light, X-ray, electron beam, and? -Ray; Molecular beams, particle beams such as ion beams, and the like. The temperature for heating the coating film is preferably 90 to 550 캜, more preferably 90 to 450 캜, and further preferably 90 to 300 캜.

The film thickness of the silicon-containing film to be formed is not particularly limited, but is preferably 100 to 20,000 nm.

The surface of the formed silicon-containing film may be subjected to methylsilylation treatment using a silylation agent or the like in order to further improve adhesion between the silicon-containing film and the resist film.

Examples of the silylating agent include aryloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, bis (trimethylsilyl) urea, trimethylchlorosilane, N - (trimethylsilyl) acetamide, trimethylsilyl azide, trimethylsilylcyananide, N- (trimethylsilyl) imidazole, 3-trimethylsilyl-2-oxazolidinone, trimethylsilyltrifluoromethanesulfonate, hexamethyl (N, N-dimethylamino) trimethylsilane, nonamethyltrisilazane, 1,1,1-trimethylsilyltrimethoxysilane, tetramethyldisilazane, hexamethyldisiloxane, 3,3-tetramethyldisilazane, trimethyl iodosilane, and the like.

The methylsilylation treatment of the surface of the silicon-containing film can be carried out, for example, by dip coating or spin-coating the above silylation treatment agent on the silicon-containing film, or by exposing the silicon-containing film to a steam atmosphere of the silylation agent. After the methylsilylation treatment, the methylsilylated silicon-containing film may be heated to 50 to 300 캜.

[(2) Process]

In the step (2), a resist composition is applied on the silicon-containing film obtained in the step (1) to form a resist film.

As the resist composition to be used, for example, a chemically amplified resist composition containing a resin whose solubility in an alkali developer is increased by the action of an acid, a positive resist composition containing an alkali-soluble resin and a quinone diazide- And a negative resist composition containing an alkali-soluble resin and a crosslinking agent. The solid concentration of the resist composition is preferably 5 to 50% by mass. The resist composition is preferably filtered using a filter having a pore diameter of about 0.2 mu m. In the above-mentioned pattern forming method, a commercially available resist composition may be used as such as the resist composition.

As a method of applying the resist composition on the silicon-containing film, for example, a conventional method such as a spin coating method and the like can be given. When the resist composition is applied, the amount of the resist composition to be applied is adjusted so that the obtained resist film has a predetermined film thickness.

At the time of forming the resist coating film, the solvent in the coating film (that is, the solvent contained in the resist composition) may be volatilized by prebaking (PB) the coating film formed by applying the resist composition. The temperature of the PB is appropriately adjusted according to the type of the resist composition to be used, and is preferably 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The time of PB is preferably 5 seconds to 600 seconds, more preferably 10 seconds to 300 seconds.

As a method of forming a resist pattern, a double patterning method or a double exposure method, which is a method of forming a fine pattern, may be suitably used. As a method of forming a resist pattern, a resist composition containing a resin whose solubility in an alkali developer is increased by the action of an acid as disclosed in Japanese Patent Application Laid-Open No. 2008-292975 is used, and as a developer A method of forming a negative pattern using an organic solvent may be used, or this method and a double exposure method may be used in combination.

[(3) Process]

In the step (3), the resist film obtained in the step (2) is selectively exposed to radiation by passing through a photomask to expose the resist film.

Examples of the radiation used for the exposure include electromagnetic waves such as visible light, ultraviolet light, deep ultraviolet light, X-ray and? -Ray, and the like depending on the kind of the acid generator used in the resist composition; Electron beams, molecular beams, particle beams such as ion beams, and the like. Of these, far ultraviolet light is preferable, and KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm), Kr ₂ excimer laser light (147 nm), ArKr excimer laser ) Light, and extreme ultraviolet light (wavelength 13 nm, etc.) are more preferable.

The method for exposing is not particularly limited, and the method can be performed in accordance with a conventionally known method for forming a pattern.

It is also preferable to perform post exposure bake (PEB) after exposure. By performing PEB, the resolution, pattern profile, developability and the like of the obtained resist pattern can be improved. The temperature of the PEB is appropriately adjusted according to the type of the resist composition to be used, and is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 150 ° C. The PEB time is preferably 5 seconds to 600 seconds, more preferably 10 seconds to 300 seconds.

[Step (4)] [

In the step (4), the resist film exposed in the step (3) is developed to form a resist pattern.

The developing solution used for development can be appropriately selected according to the kind of the resist composition to be used, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine Diethylamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1 , 8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like. These alkaline aqueous solutions may be water-soluble organic solvents such as alcohols such as methanol and ethanol, and surfactants in an appropriate amount.

Examples of the developer in the case where the resist composition to be used is the above negative resist composition include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia water, Tertiary amines such as diethylamine, di-n-butylamine and the like; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; amines such as TMAH and tetraethyl Quaternary ammonium salts such as ammonium hydroxide and choline, and aqueous solutions of alkalis such as pyrrole and piperidine.

Examples of the organic solvent as the developer for forming the negative pattern include a ketone solvent, an alcohol solvent, an ether solvent, an amide solvent, an ester solvent and the like.

Examples of the ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 2-hexanone, diisobutylketone, methyl ethyl ketone , And methyl isobutyl ketone;

Aromatic ketone solvents such as phenylacetone;

And cyclic ketone solvents such as cyclohexanone and methylcyclohexanone.

Examples of the alcoholic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n- Chain alcohol-based solvents such as heptyl alcohol, n-octyl alcohol and n-decanol;

Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol;

And glycol partial ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, Carboxylic acid esters such as methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate;

Glycol monoether acetate solvents such as propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate.

The organic solvent may be mixed with water.

As the organic solvent, an ester solvent is preferable, and butyl acetate is more preferable. The organic solvent may be used singly or in combination of plural kinds.

In the step (4), a predetermined resist pattern corresponding to the photomask can be formed by carrying out development with the developer, cleaning, and drying.

[(5) Process]

In the step (5), the silicon-containing film and the substrate to be processed are sequentially dry-etched using the resist pattern formed in the step (4) as a mask (etching mask) to form a pattern. When a processed substrate on which another resist underlayer film is formed is used, the other resist underlayer film is dry-etched together with the silicon-containing film and the substrate to be processed.

The dry etching can be performed using a known dry etching apparatus. Further, the source gas at the time of dry etching is also different, O _2, a gas containing oxygen atoms such as CO, CO ₂ according to the etched film had an elemental composition; Inert gases such as He, N ₂ , and Ar; Chlorine-based gases such as Cl ₂ and BCl ₄ ; H ₂ , NH ₃ , or the like can be used. These gases may be used alone or in combination of two or more.

By performing the above-described steps (1) to (5) in the pattern formation method, a predetermined pattern for substrate processing can be formed. By using the polysiloxane composition containing the [C] compound in addition to the [A] polysiloxane and the [B] compound as the polysiloxane composition, not only when the resist pattern is formed by the alkali development but also by the organic solvent development, A resist pattern having excellent pattern collapse resistance and good pattern shape can be formed on the silicon-containing film.

[Example]

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. The solid concentration of the polysiloxane-containing solution in this example was measured by the following method.

[Measurement of Solid Content Concentration]

0.5 g of the solution containing polysiloxane was heated at 250 캜 for 30 minutes, and the remaining mass was measured to obtain the mass of the solid component. The solid content concentration (mass%) in the solution containing polysiloxane was calculated from the value of the remaining mass.

<Synthesis of [A] polysiloxane>

The monomers used in the synthesis of [A] polysiloxane are shown below. The structure of each monomer is shown in the following formulas.

Compound (M-1): Tetramethoxysilane

Compound (M-2): phenyltrimethoxysilane

Compound (M-3): 3-ethyl-3-oxetanylmethyltrimethoxysilane

Compound (M-4): Methyltrimethoxysilane

Compound (M-5): 4-Tolyltrimethoxysilane

Compound (M-6): Tetraethoxysilane

Compound (M-7): 1,4-Bis (triethoxysilyl) benzene

[Synthesis Example 1] (Synthesis of polysiloxane (A-1)

1.28 g of oxalic acid was dissolved by heating in 12.85 g of water to prepare an oxalic acid aqueous solution. Thereafter, a dropping funnel containing a cooling tube and the oxalic acid aqueous solution prepared above was set in a flask containing 25.05 g of the compound (M-1), 3.63 g of the compound (M-2) and 57.19 g of propylene glycol monoethyl ether. Subsequently, after heating to 60 DEG C in an oil bath, an oxalic acid aqueous solution was slowly added dropwise, and the mixture was reacted at 60 DEG C for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to stand to cool and then set in an evaporator, and methanol generated by the reaction was removed to obtain 97.3 g of a solution containing the polysiloxane (A-1).

The solid content concentration in the solution containing the obtained polysiloxane (A-1) was 18.0% by mass. The Mw of the obtained polysiloxane (A-1) was 2,000.

[Synthesis Example 2] (Synthesis of polysiloxane (A-2)

2.92 g of tetramethylammonium hydroxide was dissolved by heating in 8.75 g of water to prepare a tetramethylammonium hydroxide aqueous solution. Then, a cooling tube was charged with 10.65 g of the compound (M-1), 1.98 g of the compound (M-2), and 1.65 g of the compound (M-1) in a flask containing 11.67 g of the aqueous tetramethylammonium hydroxide solution, 4.53 g of water and 20 g of methanol. M-4) and 20 g of methanol were placed in a dropping funnel. Subsequently, the mixture was heated to 50 DEG C in an oil bath, the methanol solution of the monomer was slowly dropped, and the mixture was reacted at 50 DEG C for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.

Then, the above-cooled reaction solution was added dropwise to 36.67 g of a methanol solution of maleic anhydride prepared by dissolving 4.39 g of maleic anhydride in 16.14 g of water and 16.14 g of methanol, followed by stirring for 30 minutes. Subsequently, 50 g of 4-methyl-2-pentenone was added, and then the flask was set in an evaporator to remove the reaction solvent and the methanol produced by the reaction to obtain a 4-methyl-2-pentenone solution of polysiloxane . The resulting solution was transferred to a separating funnel, and then 80 g of water was added to perform the first water washing, and 40 g of water was added to perform the second water washing. Thereafter, the 4-methyl-2-pentenone solution of the polysiloxane was transferred from the separating funnel to the flask, and then 50 g of propylene glycol monoethyl ether was added. The flask was set in an evaporator, and 4-methyl- To obtain 51 g of a solution containing the polysiloxane (A-2). The solid content concentration in the solution containing the obtained polysiloxane (A-2) was 18.0% by mass. The Mw of the obtained polysiloxane (A-2) was 4,000.

Synthesis Examples 3 to 7, 10 and 11 Synthesis of polysiloxanes (A-3) to (A-7), (A-10) and (A-

Polysiloxanes (A-3) to (A-7), (A-10) and (A-11) were synthesized in the same manner as in Synthesis Example 1 except that monomers of the kind and amount shown in Table 1 below were used. .

[Synthesis Example 9] (Synthesis of polysiloxane (A-8) and (A-9)

Polysiloxanes (A-8) and (A-9) were synthesized in the same manner as in Synthesis Example 2 except that monomers of the kinds and amounts shown in Table 1 below were used.

In each synthesis example, the solid content concentration (% by mass) of the obtained solution containing the Mw of the polysiloxane and the [A] polysiloxane is shown in Table 1 below.

&Lt; Preparation of polysiloxane composition >

Components other than the above [A] polysiloxane constituting the polysiloxane composition are shown below.

[[B] compound]

Each structure is shown in the following formula.

B-1: N-t-amyloxycarbonyl-4-hydroxypiperidine

B-2: N-t-Butoxycarbonyl-4-hydroxypiperidine

B-3: N-t-Butoxycarbonyl-3-hydroxy-5-carboxypyrrolidine

B-4: N-t-Butoxycarbonyl-2-carboxypyrrolidine

B-5: N-2,3-dihydroxypropylpiperidine

B-6: N-9-anthranylmethyloxycarbonylpiperidine

b-1: N, N ', N' ', N' '' - tetrabutoxyglycoluril

b-2: 3,12-Dihydroxy-24-nor-5? -cholan-23-acid t-butoxycarbonyl methyl ester

[[C] compound]

Each structure is shown in the following formula.

C-1: Triphenylsulfonium trifluoromethanesulfonate

C-2: Triphenylsulfonium tricyclo [3.3.1.1 ^3,7 ] decanyldifluoromethanesulfonate

C-3: Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate

[[D] solvent]

D-1: Propylene glycol monomethyl ether acetate

D-2: Propylene glycol monoethyl ether

D-3: Propylene glycol monopropyl ether

[Example 1]

9.70 parts by mass of the solution containing the polysiloxane (A-1) as the polysiloxane [A], 0.05 parts by mass of the compound (B-1) as the compound [B], 68.74 parts by mass of the compound (D- D-2) were mixed and dissolved, followed by filtration through a filter having a pore diameter of 0.2 탆 to obtain a polysiloxane composition of Example 1.

[Examples 2 to 31 and Comparative Examples 1 to 6]

Each polysiloxane composition was prepared in the same manner as in Example 1, except that the components shown in Tables 2 and 3 were used. The amount of water of component [E] means the amount of water added in the preparation of the polysiloxane composition. "-" in Table 2 and Table 3 indicates that the corresponding component is not used.

The content of water in the prepared polysiloxane composition was measured by Karl Fischer method. The values (mass%) of the water content in the obtained polysiloxane composition are shown in Table 2 and Table 3 together.

<Evaluation>

Using the polysiloxane compositions of the above Examples and Comparative Examples, a silicon-containing film was formed by the following method, and the obtained silicon-containing film was evaluated for substrate reflectance, resist residue, alkali resistance and oxygen ashing resistance by the following method I did. Further, according to the following method, the resist pattern formed on the silicon-containing film was evaluated for lithography. The evaluation results obtained are shown in Tables 4 and 5 below.

[Formation of silicon-containing film]

The polysiloxane composition was applied onto a silicon wafer by a spin coating method using a coating / developing apparatus (CLEAN TRACK ACT12, manufactured by Tokyo Electron, hereinafter referred to as an apparatus used for coating, the same apparatus was used for those not specifically described) Respectively. The obtained coating film was subjected to PB for 1 minute on a hot plate at 220 占 폚 to form a silicon-containing film. The film thickness of the obtained silicon-containing film was measured with a film thickness measuring apparatus (M-2000D, J.A. The obtained silicon-containing film was subjected to each evaluation by the following method.

[Substrate Reflectance]

(N) and the extinction coefficient (k) of the obtained silicon-containing film, the other composition for lower layer film (made by NFC HM8006, JSR) and the resist composition (made by ARF AR2772JN, JSR) (Manufactured by KLA-Tencor Co., Ltd.) on the basis of these measured values, the resist film / silicon-containing film under the condition of NA: 1.3, Dipole / Another resist underlayer film was laminated to obtain a substrate reflectance of the laminate. A "when the substrate reflectance was 1% or less, and" B "when the reflectance was more than 1%.

[Resist residue]

The resist composition was coated on the formed silicon-containing film by spin coating and then subjected to PB for 60 seconds at 100 캜 on a hot plate to form a resist film having a film thickness of 100 nm. Subsequently, the entire surface was exposed using an ArF exposure apparatus (S306C, Nikon Corporation). After the development with a 2.38 mass% TMAH aqueous solution for 1 minute, the film thickness of the film (silicon-containing film + resist film remnant) on the substrate after exposure was measured using the above film thickness measuring apparatus. The difference between the measured film thickness and the silicon-containing film before exposure was determined to calculate the resist residues. The resist residues are represented by numerical values (unit: nm). When the difference is less than 5 nm, the resist residue is good, and when the difference is 5 nm or more, it can be evaluated as defective.

[Alkali resistance]

The silicon wafer on which the silicon-containing film was formed was immersed in a TMAH aqueous solution for 1 minute, and the film thickness of the silicon-containing film before and after the treatment was measured. Quot; A "when the film thickness difference before and after the treatment was 1 nm or less, and" B "

[Resistance to oxygen ashing]

The formed silicon-containing film was subjected to O ₂ treatment at 100 W for 120 seconds using an ashing apparatus (made by NA1300, ULVAC), and the film thickness difference of the silicon-containing film before and after the treatment was measured. The film thickness difference (unit: nm) is expressed by a numerical value. When the film thickness difference is less than 5 nm, it is evaluated that the oxygen ashing resistance is good, it is slightly better when it is 5 nm or more and 8 nm or less, and it is judged that it is defective when it exceeds 8 nm.

[Lithography performance]

(In case of alkali phenomenon)

A lower antireflection film having a thickness of 100 nm was formed on a 12-inch silicon wafer by spin coating a composition for forming a lower antireflection film (made by HM8006, JSR) and then performing PB at 250 캜 for 60 seconds. The polysiloxane composition was spin-coated on the lower layer antireflection film, baked at 220 캜 for 60 seconds, and then cooled at 23 캜 for 60 seconds to form a silicon-containing film having a film thickness of 30 nm. Subsequently, a resist composition (ARF AR2772JN, made by JSR) was spin-coated on the silicon-containing film, and the film was then baked at 100 캜 for 60 seconds and then cooled at 23 캜 for 30 seconds to form a resist film having a film thickness of 100 nm. Further, a composition for forming an upper layer film was spin-coated on the formed resist film using a coating / developing apparatus (Lithius Pro-i, Tokyo Electron) and subjected to PB at 90 캜 for 60 seconds, A film was formed.

Subsequently, using an ArF liquid immersion exposure apparatus (S610C, made by Nikon Corporation), exposure was carried out through a mask having a mask size for 42 nm line / 84 nm pitch formation under optical conditions of NA: 1.30, Dipole. After PEB was performed at 100 캜 for 60 seconds on the hot plate of the above-mentioned "Lithius Pro-i ", after cooling for 30 seconds at 23 캜, paddle development was performed for 30 seconds using the TMAH aqueous solution as the developing solution with the LD nozzle of the developing cup, As a rinsing liquid. Further, diffusion was performed at 2,000 rpm for 15 seconds and spin-drying was conducted to obtain a substrate for evaluation in which a resist pattern with a 42 nm line / 84 nm pitch was formed.

When the resist pattern is formed, the exposure amount at which the line width is 42 nm and the distance (space) between adjacent lines is 84 nm (line-to-space is 1: 2) is defined as the optimum exposure amount, And the exposure was carried out successively to obtain respective substrates for evaluation.

Using these substrates for evaluation, evaluation of pattern collapse resistance and pattern shape was carried out by the following method. A scanning electron microscope (CG-4000, Hitachi High Technologies) was used for observation and length measurement of the resist pattern in these evaluations.

When the exposure amount is increased stepwise, the line width of the obtained pattern is gradually tapered, so that collapse of the resist pattern is observed at a line width corresponding to an arbitrary exposure amount. Therefore, the line width corresponding to the maximum exposure amount at which the collapse of the resist pattern is not recognized is defined as the minimum disruption dimension, and is used as an index of the pattern decay resistance. Measured values (unit: nm) of the minimum disintegration dimensions are shown in Tables 4 and 5. In Table 4 and Table 5, "-" indicates that even if the exposure amount was varied variously, pattern collapse occurred and the pattern collapse could not be evaluated. In the case where the pattern collapse resistance is not able to be evaluated even if the measured minimum collapse dimension is 40 nm or less, "A ", the minimum collapse dimension exceeds 40 nm, or the pattern collapse occurs even if the exposure amount is varied Quot; B ". The pattern shape was evaluated as "A" when there was no sag at the bottom of the resist pattern and "B" when there was pattern collapse or sagging.

(In case of organic solvent phenomenon)

In the case of the above alkali development, except for using methyl isobutyl carbinol (MIBC) as a rinsing liquid and exposing through a mask for forming a pitch of 40 nm line / 80 nm as a mask, using butyl acetate as a developing solution, An evaluation substrate on which a resist pattern was formed was obtained in the same manner as in the case of development. When the resist pattern is formed, the exposure amount at which the line width is 40 nm and the distance (space) between adjacent lines is 80 nm (line-to-space is 1: 2) is defined as the optimum exposure amount, And the exposure was carried out sequentially to obtain respective substrates for evaluation. Using the obtained evaluation substrate, the pattern decay resistance and the pattern shape were evaluated based on the above-described method and evaluation criteria.

The results of Table 4 and Table 5 show that the silicon-containing film formed of the polysiloxane composition of the example containing the [B] compound in addition to the [A] polysiloxane exhibits excellent film-like properties while maintaining the substrate reflectance, resist residues, alkali resistance and oxygen- A resist pattern excellent in pattern collapse resistance and having a good pattern shape can be formed. In addition, the polysiloxane composition further contains the [C] compound, so that the above effects are exhibited not only in the case of the alkali development but also in the case of the organic solvent development.

[Industrial applicability]

According to the polysiloxane composition and the pattern forming method of the present invention, a resist pattern having excellent pattern collapse resistance and good pattern shape can be formed. As a result, a desired pattern can be faithfully transferred to the substrate to be processed with good reproducibility. Thus, the polysiloxane composition, and a pattern forming method to form a pattern using a multi-layer resist process in (ArF, F _2, EUV, nano-imprint in ArF, immersion exposure) the multi-layer resist pattern with a step formation, particularly fine region than 60nm Can be suitably used.

Claims (14)

[A] polysiloxane, and
(B) a compound having a nitrogen-containing heterocyclic structure and an ester group having a group represented by the following formula (i) and having a group bonded to a nitrogen atom
By weight based on the total weight of the resist underlayer film forming composition.

(Wherein R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, provided that R ¹ and R ² are bonded to each other, Together with the carbon atoms to which they are bonded, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, and * denotes a bonding site with a nitrogen atom) The polysiloxane composition for forming a resist lower layer film according to claim 1, further comprising a compound capable of generating an acid by at least one of [C] irradiation with ultraviolet rays and heating. The polysiloxane composition for forming a resist lower layer film according to claim 1, wherein the [B] compound further has a polar group. 4. The polysiloxane composition according to claim 3, wherein the polar group is a compound having at least one kind of group selected from the group consisting of a hydroxyl group and a carboxyl group. delete The polysiloxane composition for forming a resist underlayer film according to claim 1, wherein the compound [B] is a compound represented by the following formula (1).

(Wherein R ¹ , R ² and R ³ are the same as in the above formula (i), Z is an (n + 2) -valent group forming a heterocyclic structure together with the nitrogen atom, A is a single bond Or a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁴ is a hydroxyl group or a carboxyl group, n is an integer of 1 to 6, and when A and R ⁴ each are plural, a plurality of A and R ⁴ are each the same or different You can do it) The resist underlayer film-forming polysiloxane composition according to claim 1, wherein the polysiloxane [A] comprises a hydrolyzed condensate of a compound represented by the following formula (S-1).

(In the formula (S-1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, an alkenyl group or an aryl group, and a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, X is a halogen atom or OR ^A , R ^A is a monovalent organic group, a is an integer of 0 to 3, with the proviso that R ⁵ and X are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, A plurality of R &lt; ⁵ &gt; s and X's may be the same or different, The polysiloxane composition for forming a resist lower layer film according to claim 7, wherein X in the formula (S-1) is OR ^A. The polysiloxane composition for forming a resist lower layer film according to claim 1, wherein the content of the [B] compound relative to 100 parts by mass of the [A] polysiloxane is 0.1 part by mass or more and 30 parts by mass or less. The polysiloxane composition according to claim 2, wherein the content of the [C] compound relative to 100 parts by mass of the [A] polysiloxane is 0.1 part by mass or more and 30 parts by mass or less. The polysiloxane composition for forming a resist lower layer film according to claim 1, further comprising [E] water. delete (1) a step of applying the resist underlayer film-forming polysiloxane composition of claim 1 onto a substrate to form a silicon-containing film,
(2) a step of applying a resist composition on the silicon-containing film to form a resist film,
(3) a step of selectively exposing the resist coating film by irradiating the photomask with radiation,
(4) a step of developing the exposed resist film to form a resist pattern, and
(5) a step of sequentially dry-etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask
&Lt; / RTI &gt; 14. The pattern forming method according to claim 13, wherein the resist underlayer film-forming polysiloxane composition further comprises a compound which generates an acid by at least one of [C] irradiation with ultraviolet rays and heating.